Hydroxyphenyl urethanes

ABSTRACT

Urethanes consisting of a 2-hydroxy-1,1&#39;&#39;-diphenyl ketone having an R-NH-CO-0- group in 4-position and wherein R e.g. represents an alkyl or an aryl radical. These urethanes are useful as stabilizers for organic material and above all as agents for combatting harmful micro-organisms.

United States Patent [7 2] Inventors Max Duennenberger Frenkendorf; Max Schellenbaum, Muttenz, both of Switzerland [2|] Appl. No. 742,173 [22] Filed July 3, 1969 [45] Patented Nov. 23, 1971 [73] Assignee CIBA Limited Basel, Switzerland [32] Priority July 11, 1967 [3 3] Switzerland [3 l 9948/67 [54] HYDROXYPHENYL URETHANES 8 Claims, No Drawings [52] US. Cl .j. 260/471 C,

Int. Cl

[50] Field of Search 260/471 C, 482 C, 468 C [56] References Cited UNITED STATES PATENTS 3,458,639 7/1969 Heiss et al 260/471 Primary Examiner-Lewis Gotts Assistant Examiner-L. Arnold Thaxton Attorneys-Harry Goldsmith, Joseph G. Kolodny, Bryant W.

Brennan and Edward 1. Sites ABSTRACT: Urethanes consisting of a 2-hydroxy-l,l

diphenyl ketone having an R-NHCO0 group in 4-position and wherein R e.g. represents an alkyl or an aryl radical. These urethanes are useful as stabilizers for organic material and above all as agents for combatting harmful micro-organlSmS.

HYDROXYPHENYL URETHANES The subject of the present invention are new urethanes of general formula II C wherein X denotes a hydrogen atom. a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group, Y denotes a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, or a R--NH-CO-O residue, Z denotes a hydrogen atom, a halogen atom, an alkyl group or a .phenyl group, and R denotes an alkyl, halogenalkyl, alkenyl or cycloalkyl group or an optionally substituted phenyl group. In the case where R represents a substituted phenyl group, preferred substituents are a halogen atom, a halogenalkyl group, an alkyl group or an alkoxy group.

Preferred urethanes correspond to the formula wherein X, denotes a hydrogen atom, a halogen atom, a hydroxyl group or an alkyl group having one to four carbon atoms, Y, denotes a hydrogen atom, a halogen atom, a hydroxyl group or an R,NH--CO-O- residue, Z, denotes a hydrogen atom, a halogen atom, a phenyl group or an alkyl group having one to four carbon atoms and R, denotes an alkyl group having one to 12 carbon atoms or a residue of formula wherein U and V each denote a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having one to four carbon atoms or an alkoxy group.

Amongst the urethanes of formula (2), compounds of formulas (3) to (5) below demand very especial interest:

to the formula Amongst the urethanes of formulas (3) to (5), the urethanes of formula wherein U and V have the significance mentioned. are in turn very especially preferred. Urethanes which are derived from formula (7) for example correspond to the formulas The urethanes of formula l may be obtained according to the usual processes for obtaining urethanes.

The urethanes of formula l are manufactured by reacting 1 mol of a compound of formula with l or 2 mols of a compound of formula (13) RB wherein A and B denote residues which are able to form the bridge Ofi-NH by condensation or addition, and R, X, Y and 2 have the significance mentioned.

An embodiment of this process consists of reacting a phenol of formula X E I Y ll with an isocyanate of formula l) R-NCO wherein R, X, Y and Z have the significance mentioned.

Depending on the starting products and molar ratios, the reaction can for example take place in accordance with the following scheme:

OH ii 1 I R-NCO OH Preferably isocyanates are reacted with appropriate phenols. The phenols used as starting substances are either known or can be manufactured according to methods which are in themselves known. The following are for example used as isocyanates: 4-chloro-3-trifluoromethylphenyl isocyanate. 3.5-

, di-(trifluoromethyl)phenyl isocyanate, 3,4-di-(chloro)-phenn=1or2 l H RN (H) (l-n) Urethane of formula l HCl The urethanes of formula (1) simultaneously show two effects, namely as stabilizers and. above all as agents for combatting harmful microorganisms. The urethanes of formula (I) may accordingly be used as stabilizers for organic materials, for example as protection agents against ultraviolet radiation and oxidation influences. and simultaneously especially as materials for combatting harmful micro-organisms on or in these organic materials. The organic materials are thereby protected against the harmful action of micro-organisms and/or optionally of ultra violet radiation, warmth, air and ox- 0 the same time the freedom from odor and color of the urethanes of formula l is of particular value in respect of use technology. The present invention thus also comprises their use for pest control quite generally. This use is possible on a very broad basis, especially for protecting organic substrates against attack by destructive and pathogenic (including phytopathogenic) micro-organisms. The compounds of formula 1 are accordingly suitable for use both as preservatives and as disinfectants for textiles and technical products of all kinds, in plant protection, in agriculture, in veterinary medicine and in cosmetics.

Amongst the technical products which can be preserved with the aid of compounds of formula (1 the following may be selected as examples: textile auxiliary agents or finishing agents, glues, binders. paints, color pastes or printing pastes and similar preparations based on organic and inorganic dyestuffs or pigments, including those which contain casein or other organic compounds as admixtures. Wall and ceiling paints, for example those containing a color binder which contains albumen, are also protected against attack by pests by an addition of the new compounds. It is also possible to use them for timber protection.

Furthermore, compounds of formula I) may be used for a preservative and disinfectant finish of fibers and textiles. wherein they may be applied to natural and synthetic fibers and there display a lasting effect against harmful (including pathogenic) organisms, for example fungi and bacteria. In this, the addition may be effected before, simultaneously with. or after treating these textiles with other substances, for example color or printing pastes, finishes and the like.

Textiles treated in this way also show protection against the occurrence of perspiration odor such as is occasioned by micro-organisms.

The compounds of formula I) may also be used as preservatives in the cellulose and paper industry, interalia for preventing the known slime formation, caused by micro-or ganisms, in the equipment used for obtaining paper.

Furthennore combination of compounds of formula l) with detergentlike or surface-active substances leads to washing and cleaning agents having excellent antibacterial or antimycotic action. The compounds of formula l may for example be incorporated into soaps, or combined with soap-free detergentlike or surface-active substances or with mixtures of soaps and soap-free detergentlike substances, with their antimicrobial activity remaining fully preserved in these combinations.

Cleaning agents containing compounds of formula I) may be employed in industry and in the household, and also in the foodstuff industry, for example in dairies, breweries and abattoirs. The urethanes of formula l may also be used as a constituent of preparations which are used for cleaning or disinfection purposes.

The action can also be utilized in preservative and disinfectant finishes of plastics. When using plasticizers it is advantageous to add the compounds of formula l to the plastic with the compounds dissolved or dispersed in the plasticizer. It is appropriate to ensure that the material is as uniformly distributed in the plastic as possible. The plastics having antimicrobial properties may be used for utensils of all kinds in which effectiveness against the most diverse germs, such as for example bacteria and fungi, is desired, as for example in doormats, bathroom curtains, toilets, foot grids in swimming baths, and wall coverings. The incorporation in wax and polishing compositions results in floor polishes and furniture polishes having a disinfectant action.

The compounds of formula (I) may be applied to textile materials to be protected in the most diverse manner, for example by impregnation or spraying with solutions or suspensions which contain the compounds mentioned as the active substance. The active substance content may herein, depending on the end use, lie at between I and 30 g. of active substance per liter of treatment liquid. In most cases textile materials of both synthetic and natural origin are adequately protected against attack by fungi and bacteria by a content of 0.1 to 3 percent of active substance. The active substance may be employed together with other textile auxiliary agents such as finishing agents, crease-proof finishes and the like.

The use forms can correspond to the usual formulations of pesticides; for example, agents containing a compound of formula 1) may optionally further also contain additives such as carriers, solvents, diluents, dispersing agents, wetting agents or adhesives and the like, as well as other pesticides.

It is also possible, in principle, by means of the compounds described under formula l to stabilize and protect all those organic materials which are in any way damaged or destroyed by the influence of ultraviolet radiation. Such damage by the action of the same cause, namely ultraviolet radiation, can have very diverse results, for example color change, change in mechanical properties (brittleness, tendency to crack, tear strength, flexural strength, abrasion resistance, elasticity and ageing), the initiation of undesired chemical reactions (decomposition of sensitive chemical substances, for example medicines, photochemically induced rearrangements, oxidation and the like (for example of oils containing unsaturated fatty acids), the inducing of burn phenomena and irritations (for example in the case of human skin) and many others. Great importance attaches to the use of the compounds of formula l) for protecting polycondensation products and polyaddition products against the action of ultraviolet. Furthermore a whole series of the compounds defined above also shows, alongside the said ultraviolet protective action, a stabilizing effect against the action of oxygen and heat.

The organic materials to be protected may be in the most diverse processing states and states of aggregation, whilst their common characteristic consists of a sensitivity towards ultraviolet radiation.

Where the protective agents of formula l) which are to be used are to be employed for the treatment of organic textile materials of natural or synthetic origin, for example textile fabrics, they may for this purpose be applied to the substrate to be protected by fixing processes resembling dyeing processes in each phase of the final processing, such as finishing, crease-proofing, dyeing processes or other finishing.

The new stabilizing agents of formula (1) which are to be used are preferably added to, or incorporated in, the materials before or during their shaping. Thus they may for example, in the case of the manufacture of films, foils, strips or shaped articlet, be added to the compression-moulding or injectionmoulding composition or be dissolved, dispersed or otherwise finely divided in the spinning composition before spinning. The protection agents may also be added to the starting substances, reaction mixtures or intermediates for the manufacture of fully synthetic or semisynthetic organic materials, thus also including addition before or during the chemical reaction, for example in the case of a polycondensation (thus also to precondensates), in a polymerization (thus also to prepolymers) or in a polyaddition.

It is obvious from the foregoing that in addition to the protection of the substrate or the carrier substance which contains the ultraviolet absorption agent, the protection of other concomitant substances of the substrate is also simultaneously achieved, for example of dyestuffs, antioxidants, disinfectant additives, antistatic agents and other finishes, plasticizers and fillers.

Depending on the nature of the substance to be protected or stabilized, and on its sensitivity or the form of protection and stabilization in respect of application technology. the requisite quantity of stabilizer may vary between wide limits, for example between about 0.0] to 10 percent by weight relative to the amount of substrate to be protected. For most practical purposes amounts of about 0.05 to 2 percent however suffice. v The process for protection of organic materials against the action of ultraviolet radiation and heat which results from the foregoing thus consists of homogeneously distributing the compounds defined above in the organic materials to be protected, applying them to the surface of these materials or coating the materials to be protected by a filter layer which contains the compounds described.

If the substance of formula l) which is to be used is to be applied to the surface of the substrate to be protected, such as for example a fiber material (fabric), then this can advantageously be effected by introducing the substrate to be protected into a liquor which contains the ultraviolet absorption agent in a dissolved or dispersed form. Suitable solvents may for example be methanol, ethanol, acetone, ethyl acetate, methyl ethyl ketone, cyclohexanol or especially water. The substrate to be treated is, similarly to the case of dyeing processes, left in the liquor at 10 to 120 C. for a certain time-l0 minutes to 24 hours sufiice in most cases-it being possible optionally to agitate the liquor at the same time. Thereafter the material is rinsed, optionally washed and dried.

The parts and percentages mentioned in the examples which follow are units by weight.

EXAMPLE l 10.7 parts of 2,4-dihydroxy-benzophenone are dissolved in l50 parts of benzene at C. After adding 0.2 parts of L4- diazabicyclo-[ 2,2,21-octane, l 1.1 parts of 4-chloro-5- trifluoromethyl-phenyl-isocyanate are added dropwise over Legend t; Table I:

Column I=F0rmula number Column II=A in formula Column III=R ll Column IV=Melting point in C.

TABLE 1 Determination of the minimal inhibitory concentration (MIC) against bacteria and fungi in the dilution test.

The determination of the MIC (minimal inhibitory concentration) is efl'ected according to a test derived from Standard Specifications, which permits an approximation to absolute minimal inhibitory values of an active substance.

An 0.4 percent strength, and an 0. l2 percent strength solution in dimethyl sulfoxide are produced from the active substances. 0.25 ml. of the respective solutions are added to 9.75 ml. of sterile Brain Heart infusion Broth (bacteria) or beer wort solution (fungi). The two series obtained by progressive dilution by ten-fold in each case are combined and thereby convened to the following continuous dilution series:

100, 30, i0, 3 and l p.p.m. of active substance.

The solutions are inoculated with the bacterium Staphylococcus aureus and the fungus Rhizopus nigricans. Thereafter incubation is effected for 48 hours at 37 C. in the case of the bacterium (bacteriostasis) and for 72 hours at C. in the case of fungus (fungistasis).

After the times mentioned, the minimal inhibitory values (p. .m.) of table ii are found.

TABLE II Minimal inhibitory concentration (MIC) I II III IV I 6LT. a I 1 W (51 zoo-2 10 33 Same as above $1; 197-198 34 ..d0 CFs 198-199 a C F:

36 Same as above 163-164 Ha? H;C(i3

HaC

C1-NHC o-o- 38 (|)H (J Fr 199-200 51 NH-CO-O or;

EXAMPLE 2 EXAMPLE 3 A film of approximately 60 a thickness is manufactured from a l0 percent strength acetone solution of acetylcellulose which contains 2 percent of the compound of formula (9), calculated relative to acetylcellulose. After drying the following values are obtained for the percentage light transmission.

TABLE III Light transmission in percent Exposed to light Wavelengths Not exposed hours in m to light Fadeomcter) Similar results are for example obtained with the compounds of formulas (8), l0), (1 l) or other compounds according to the invention mentioned in the description, provided these compounds are dissolved in the acetylcellulose.

EXAMPLE 4 Pasteur pipette.

After 24 hour incubation at 37 C. the length of the germs which have grown on the inoculation line is measured and expressed in p.p.m. of active substance. The following results were obtained by this test method:

Samples of 100 g. cotton cretonne are impregnated at 20 C., on a padding machine, with an 0.1 percent strength isopropanol or dioxane solution of the compounds of formula (I) and subsequently squeezed out with l percent liquor uptake.

The fabrics dried at 30 to 40 C. contain 0.1 percent of active substance relative to their own weight.

In order to test the action against bacteria, mm. diameter discs of the impregnated fabrics, unsoaked and after soaking, are laid for 24 hours at 29 C. onto Brain Heart infusion Agar plates which are inoculated beforehand with Staphylococcus Eureus. The plates are thereafter incubated for 24 hours at 37 The inhibitory zone (Hz. in mm.) occurring around the discs is assessed on the one hand, and the microscopically determinable growth (W in percent) under the fabric or on the fabric is assessed on the other hand.

1. A urethane of the formula wherein X represents a hydrogen atom, a chlorine atom, a hydroxyl group and an alkyl group having one to four carbon atoms, Y represents a hydrogen atom, a chlorine atom, a hydroxyl group, an alkyl group having one to four carbon atoms, a methoxy group and an RNH-CO)- radical, Z represents a hydrogen atom, a chlorine atom, a phenyl group and an alkyl group having one to four carbon atoms and R denotes a member selected from the group consisting of an alkyl group having one to 12 carbon atoms alkenyl having two to four carbon atoms and a radical of the formula wherein U, V and W each represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having one to four carbon atoms and an alltoxy group having one to four carbon atoms.

2. A urethane according to claim 1 wherein W is hydrogen and U and V each represents a member selected from the group consisting of a hydrogen atom, a halogen atom a trifluoromethyl group, a methyl group and a methoxy group.

3. A urethane according to claim 1 of the formula x on 0 II C Y OCONH-R wherein X represents a hydrogen atom or a hydroxyl group, Y represents a member selected from the group consisting of a hydrogen atom, a chlorine atom, a methoxy group, a phenyl group, an alkyl group having one to four carbon atoms and an R-NHCO-O radical and R denotes a member selected from the group consisting of an alkyl group having one to 12 carbon atoms, an alkenyl group having two to four carbon atoms and a radical of the formula wherein U, V and W each represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having one to four carbon atoms and an alkoxy group having one to four carbon atoms.

4. A urethane according to claim I of the formula wherein U and V each represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a

trifluoromethyl group. a methyl group and a methoxy group.

5. The urethane according to claim 1 of formula on fim 6; The urethane according to claim 1 of formula 7. The urethane according to claim 1 of formula 8. The urethane according to claim 1 of formula CASE 6223/E 5 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,622,618 Dated November 23, 1971 Inventofls) MAX DUENNENBERGER ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Patent No.

Column 11, line 57, change "R-NH-CO-)-" to read R-NH-CO-O- Column 12, claim 6 in the formula, change "CF3" to Signed and sealed this 13th day of June 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

2. A urethane according to claim 1 wherein W is hydrogen and U and V each represents a member selected from the group consisting of a hydrogen atom, a halogen atom, a trifluoromethyl group, a methyl group and a methoxy group.
 3. A urethane according to claim 1 of the formula
 4. A urethane according to claim 1 of the formula
 5. The urethane according to claim 1 of formula
 6. The urethane according to claim 1 of formula
 7. The urethane according to claim 1 of formula
 8. The urethane according to claim 1 of formula 